[1ChCl∶2EG]/CrCl3·6H2O离子液体中Cr(Ⅲ)配合物的研究

利用电喷雾质谱(ESI-MS)和紫外-可见吸收光谱(UV-Vis)分析,研究了CrCl₃·6H₂O 浓度为0.1～0.6 mol·L-1的水溶液和[1ChCl∶2EG]/CrCl₃·6H₂O ILs中,Cr(Ⅲ)配合物的存在形式。研究结果表明,在含有CrCl₃·6H₂O的溶液中,Cr(Ⅲ)与Cl-和H₂O形成[Cr(H₂O)_nCl_6-n]n-3配合物,其配合物的优势物种受CrCl₃·6H₂O浓度的影响。水溶液中Cr(Ⅲ) 的优势配合物为[Cr(H₂O)₆]3+与[Cr(H₂O)₅Cl]2+,并随CrCl₃·6H₂O浓度增加,水溶液的UV-Vis吸收光谱峰红移,[Cr(H₂O)₅Cl]2+的相对含量增加。而[1ChCl∶2EG]/CrCl₃·6H₂O ILs中的优势配合物为[Cr(H₂O)₂Cl₄]-和[Cr(H₂O)₃Cl₃],且随CrCl₃·6H₂O 浓度增加,溶液的颜色从浅橙红色逐渐变为深绿色,溶液的UV-Vis吸收光谱峰蓝移,[Cr(H₂O)₃Cl₃]的相对量增加。说明CrCl₃·6H₂O的浓度变化,将影响配体Cl-和H₂O与Cr(Ⅲ)配位结合的配位数,从而影响配合物优势物种的相对量。     

浅埋偏压连拱隧道现场监测与结构受力分析研究

针对浅埋偏压连拱隧道结构受力的复杂性,结合石红高速大中山1#连拱隧道的实际情况,选择典型断面埋设监控量测设备对隧道施工过程中围岩变形和结构受力进行适时监测,并结合有限元分析软件MIDAS,对中隔墙空间受力特征进行研究.得出了支护结构在偏压作用下和施工扰动下的受力状态和变形特征.结果表明,在浅埋偏压条件下,减少支护结构受力的不均对于保证隧道结构稳定的重要性以及运用监控量测与数值模拟相互印证的方法可以更准确地分析隧道结构的稳定性,更好地指导施工.     

Electronic structure of O-doped SiGe calculated by DFT+U method

To more in depth understand the doping effects of oxygen on Si Ge alloys, both the micro-structure and properties of O-doped Si Ge(including: bulk,(001) surface, and(110) surface) are calculated by DFT + U method in the present work.The calculated results are as follows.(i) The(110) surface is the main exposing surface of Si Ge, in which O impurity prefers to occupy the surface vacancy sites.(ii) For O interstitial doping on Si Ge(110) surface, the existences of energy states caused by O doping in the band gap not only enhance the infrared light absorption, but also improve the behaviors of photo-generated carriers.(iii) The finding about decreased surface work function of O-doped Si Ge(110) surface can confirm previous experimental observations.(iv) In all cases, O doing mainly induces the electronic structures near the band gap to vary, but is not directly involved in these variations. Therefore, these findings in the present work not only can provide further explanation and analysis for the corresponding underlying mechanism for some of the experimental findings reported in the literature, but also conduce to the development of μc-Si Ge-based solar cells in the future.     

Spectroscopic properties and mechanism of Tm^3＋/Er^3＋/Yb^3＋ co-doped oxyfluorogermanate glass ceramics containing BaF2 nanocrystals

Transparent Tm^3＋/Er^3＋/yb^3＋ co-doped oxyfluorogermanate glass ceramics containing BaF2 nanocrystals are prepared. Under excitation of a 980-nm laser diode （LD）, compared with the glass before heat treatment, the Tm^3＋/Er^3＋/yb^3＋ co-doped oxyfluorogermanate glass ceramics can emit intense blue, green and red up-conversion luminescence and Stark- split peaks; X-ray diffraction （XRD） and transmission electron microscope （TEM） results show that BaF2 nanocrystals with an average diameter of 20 nm are precipitated from the glass matrix. Stark splitting of the up-conversion luminescence peaks in the glass ceramics indicates that Tm^3＋, Er^3＋ and （or） Yb^3＋ ions are incorporated into the BaF2 nanocrystals. The up-conversion luminescence intensities of Tm^3＋, Er^3＋ and the splitting degree of luminescence peaks in the glass ceramics increase significantly with the increase of heat treat temperature and heat treat time extension. In addition, the possible energy transfer process between rare earth ions and the up-conversion luminescence mechanism are also proposed.     

Electronic structures of halogen-doped Cu20 based on DFT calculationsElectronic structures of halogen-doped Cu20 based on DFT calculationsElectronic structures of halogen-doped Cu20 based on DFT calculations

In order to construct p-n homojunction of Cu20-based thin film solar cells that may increase its conversion efficiency, to synthesize n-type Cu20 with high conductivity is extremely crucial, and considered as a challenge in the near future. The doping effects of halogen on electronic structure of Cu20 have been investigated by density function theory calculations in the present work. Halogen dopants form donor levels below the bottom of conduction band through gaining or losing electrons, suggesting that halogen doping could make Cu20 have n-type conductivity. The lattice distortion, the impurity formation energy, the position, and the band width of donor level of Cu201-xHx （H = F, C1, Br, I） increase with the halogen atomic number. Based on the calculated results, chlorine doping is an effective n-type dopant for Cu20, owing to the lower impurity formation energy and suitable donor level.     

Photoluminescence characteristics and energy transfer between Bi~（3＋） and Eu~（3＋） in Na_2O–CaO–GeO_2–SiO_2 glass

We report the photoluminescence（PL） of Eu^3＋-doped glass with Bi^3＋as a sensitizer. The specific glass system with the strong enhancement of the red emission of Eu3＋is obtained by adding a small number of Bi3＋ions instead of increasing the Eu^3＋ concentration. The emission band of Bi3＋overlaps with the excitation band of Eu^3＋ and the lifetime decay curves,resulting in a very efficient energy transfer from Bi^3＋ to Eu^3＋. The probability of energy transfer is strongly dependent on Bi^3＋ concentration. In addition, the intensity of 4f–4f transition is much stronger than that of a charge-transfer（CT） band in the excitation spectrum, which indicates that the Na2O–Ca O–Ge O2-Si O2 glass is a suitable red-emitting phosphor with high stability as a candidate for light-emitting diodes（LEDs）.     

ChemInform Abstract: Electronic Structure,Elastic Anisotropy,Thermal Conductivity and Optical Properties of Calcium Apatite Ca5(PO4)3X (X: F,Cl or Br).

The structural properties, phase stability, electronic structure, elastic properties, and optical properties of Ca₅(PO₃)₄F (FA), Ca₅(PO₃)₄Cl (ClA) and Ca₅(PO₃)₄Br (BrA) are studied by DFT calculations with the generalized gradient approximation.     

大尺寸物光波面彩色数字全息高质量重建研究

为解决检测面尺寸较大时CCD难以得到高质量数字全息图的问题,本文利用负透镜设计光学系统让CCD接收来自物体的缩小虚像,以球面波为参考波,使用单色CCD近距离得到三种色光照射下的大尺寸彩色物体的数字全息图,然后采用可控放大率波面重建算法得到同一尺寸的数字全息重建像,合成彩色数字全息重建像.同时,使用两种消零级方法去除零级干扰,提高重建像质量,一种方法利用空间光调制器相移技术在参考光中加入一次任意相移,记录两幅数字全息图,消除重建零级像|另一种方法使用“无干扰全息图”消除重建零级像及共轭像.本文讨论结果可为大物体彩色数字全息及多波长数字全息检测应用提供有益的参考.     

像面滤波技术在无透镜傅里叶变换数字全息中的应用

无透镜傅里叶变换数字全息波前重建主要采用全息图的一次快速傅里叶变换方法,重建图像不能充分占有重建平面.本文基于像平面滤波技术,提出对物体局部区域光波场进行放大重建并让重建图像布满重建平面的方法,给出具有精细结构物体的数字全息波前重建实例.此外,将数字全息光波场重建视为具有方形出射光瞳的光学系统的相干光成像过程,导出了物体放大图像的分辨率与光学系统相关参量的关系,并通过实验给予证明.     

Interfacial electronic structure and magnetoelectric effect in M/BaTiO3 (M=Ni,Fe) superlattices

Using first-principles density functional theory, we investigate the interfacial electronic structure and magnetoelectric effect in M/BaTiO₃ (M=Ni, Fe) superlattices, and find a novel type of interfacial magnetoelectric coupling mechanism in the Ni/BaTiO₃ interface. This magnetoelectric effect is determined by the change of magnetic moments on Ni atoms near the interface, instead of the induced moments on interfacial Ti atoms in Fe/BaTiO₃ system, which is also distinguished from the spin-polarized carriers screening mechanism. The underlying physics is the strong interface bonding and the pdσ-type magnetic interactions between Ni 3d and O 2p spins. Furthermore, there exists an extraordinary intralayer oscillation of magnetic moments within the Ni layers, which may be observed in experiments.